Structure and Bonding 1

STRUCTURE & BONDING

Introduction The physical properties (boiling point, conductivity, strength) of a substance
depend on its structure and type of bonding. Bonding determines the structure.

TYPES OF BOND

CHEMICAL BONDS • IONIC (or electrovalent)

(strong bonds) • COVALENT
• DATIVE COVALENT (or COORDINATE)
• METALLIC

weakest
PHYSICAL BONDS • induced dipole-dipole interactions (London forces)
(weak bonds) • permanent dipole-dipole interactions
(both the above are examples of van der Waals‘ forces)
• hydrogen bonds
strongest

FORMATION OF IONS FROM ATOMS

Positive ions • known as cations

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• formed when electrons are removed from atoms

• are smaller than the original atom
• the energy associated with the process is known as the ionisation energy (IE).

1st I.E. The energy required to remove one mole of electrons (to infinity) from one mole of
gaseous atoms to form one mole of gaseous positive ions.

e.g. Na(g) ——> Na+(g) + e¯ or Mg(g) ——> Mg+(g) + e¯

There are as many ionisation energy steps as there are electrons in the atom.

2nd I.E. Mg+(g) ——> Mg2+(g) + e¯ and so on

Notes • successive ionisation energies get larger as the proton : electron ratio increases.
3rd ionisation energy > 2nd ionisation energy > 1st ionisation energy

• big jumps in value occur when electrons are removed from shells nearer the
nucleus - less shielding so more energy is needed to overcome the attraction.

1st I.E 500 kJmol-1 2nd I.E 900 kJmol-1 3rd I.E 6000 kJmol-1
The 3rd electron must have been in a shell nearer the nucleus - In Group 2

• if the IE values are very high, covalent bonding is favoured (e.g. beryllium).

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2 Structure and Bonding

Negative ions • known as anions

• larger than the original atom due to electron repulsion in outer shell
• formed when electrons are added to atoms
• energy is released as the nucleus pulls in an electron
• this energy is the electron affinity.

Electron
Affinity The energy change when one mole of gaseous atoms acquires one mole of
electrons (from infinity) to form one mole of gaseous negative ions.

e.g. Cl(g) + e¯ ——> Cl¯(g) and O(g) + e¯ ——> O¯(g)

The greater the effective nuclear charge (ENC) the easier an electron is pulled in.

Q.1 Write out equations representing the ....

• 1st I.E. of Li
• 1st I.E. of Al

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• 1st I.E. of F
• 2nd I.E. of Na
• 2nd I.E. of F
• 3rd I.E. of Li
• 4th I.E. of Al
• 21st I.E. of Rb

Q.2 Write out equations representing the ....

• 1st E.A of Br
• 2nd E.A of Br
• 1st E.A. of N

Q.3 In which group would you find elements with the following successive I.E.’s ?

• 577 1820 2740 11600 14800

• 418 3070 4600 5860 7990
• 736 1450 7740 10500 13600

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 Structure and Bonding 3

THE IONIC (OR ELECTROVALENT) BOND

‘An electrostatic attraction between postive and negative ions’

Formation Ionic bonds tend to be formed between elements whose atoms need to “lose”
electrons to gain the nearest noble gas electronic configuration (ngec) and those
needing to gain electrons. Electrons are transferred from one atom to the other.

Sodium Na ——> Na+ + e¯ and Cl + e¯ ——> Cl¯

Chloride 1s2 2s2 2p6 3s1 1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 3s2 3p6
or 2,8,1 2,8 2,8,7 2,8,8

11+ 17+ 17+

11+

Na (2,8,1) Cl (2,8,7) Na+ (2,8) Cl- (2,8,8)

• 1 electron is transferred from the 3s orbital of sodium to the 3p orbital of chlorine

• both species end up with an ‘octet’ of electrons in their outer shell
• the resulting ions are held together in a crystal lattice by electrostatic attraction
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MgCl2 Because magnesium atoms have two outer shell electrons they can combine with
two chlorine atoms by the transfer of one electron to each atom to form one Mg2+
and two Cl¯ ions

17+ 17+

12+
12+

17+ 17+

-
Mg (2,8,2) 2 x Cl (2,8,7) Mg 2 + 2 x Cl

Q.4 Show how the following combine to form ionic compounds.

a) Na and O b) Mg and O c) Mg and F d) Al and O

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4 Structure and Bonding

Predicting the charge on an ion

Simple ions

s an p block Can be predicted from their position in the Periodic Table

elements
Group electrons in outer shell charge on ion
1 1 +
2 2 2+
3 3 3+
6 6 2-
7 7 -

d block Transition elements (eg iron) can have more than one ion. The use of a
elements Roman numeral identifies which ion is present.

iron(II) Fe2+ iron(III) Fe3+

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Complex ions Some groups possess a charge.

nitrate NO3¯ sulphate SO42-

carbonate CO32- ammonium NH4+

SOME COMMON IONS

hydrogen H+ chloride Cl¯

sodium Na+ bromide Br¯
potassium K+ iodide I¯
1 lithium Li+ hydroxide OH¯
rubidium Rb+ nitrate NO3¯
caesium Cs+ nitrite NO2¯
copper(I) Cu+ hydrogencarbonate HCO3¯
silver(I) Ag+ hydrogensulphate HSO4¯
ammonium NH4+

calcium Ca2+ sulphate SO42-

barium Ba2+ sulphite SO32-
magnesium Mg2+ sulphide S2-
2 zinc Zn2+ oxide O2-
iron(II) Fe2+ carbonate CO32-
cobalt Co2+ copper(II) Cu2+
manganese(II) Mn2+

3 aluminium Al3+ phosphate PO43-

iron(III) Fe3+

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 Structure and Bonding 5

GIANT IONIC LATTICES

bonding • oppositely charged ions held in a regular 3-d lattice by electrostatic attraction
• ions pack together in the most efficient way so there is little wasted space
• the arrangement of ions in a lattice depends on the relative sizes of the ions

NaCl CsCl

The Na+ ion is small enough relative to the Cl¯ ion to fit in the spaces so that both
ions occur in every plane.

Each Na+ is surrounded by 6 Cl¯ (co-ordination number = 6) and each Cl¯ is

surrounded by 6 Na+ (co-ordination number = 6).

Physical properties of ionic compounds

melting pt Very high A large amount of energy must be put in to overcome the
strong electrostatic attractions and separate the ions.
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strength Very brittle Any dislocation leads to layers moving and similarly charged
ions being next to each other. The repulsion splits the crystal.

electrical • do not conduct electricity when solid - ions are held strongly in the lattice
• conduct electricity when molten or in aqueous solution - the ions
become mobile and conduction takes place.

solubility • insoluble in non-polar solvents

• soluble in water as it is a polar solvent and stabilises the separated ions
• energy is needed to overcome the electrostatic attraction and separate the ions
• stability is achieved by polar water molecules surrounding the ions

Diagram

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6 Structure and Bonding

COVALENT BONDING

Definition • consists of a shared pair of electrons; each atom supplies one electron
• atoms are held because their nuclei are attracted to the shared electrons

positive nucleus nucleus of other atom

attracts shared pair is also attracted to the
+ + shared pair

• Average bond enthalpy is a measurement of the strength of a covalent bond

the stronger the bond, the higher its value ( see later work )

Formation • between atoms of the same element; (N2, O2, diamond and graphite)
• between atoms of different elements on RHS of the periodic table; (CO2, SO2).
• when one of the elements is in the middle of the table; (e.g. C, Si)
• head-of-the-group elements with high ionisation energies, (e.g. Be in BeCl2)

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METHANE H H H

O
X
X X
C H C H H O C O H

O
X
H H H
H "dot and cross"
needs four four covalent single diagram
each needs one electron electrons bonds are formed

OO
WATER H—O—H
H H
O H O OO

OO
X O
H
H O OO
XO
H

• atoms share electrons in order to complete their ‘octet’ of electrons

• some don’t achieve an ‘octet’ as they haven’t enough electrons - Al in AlCl3
• others share only some - if they share all their ‘octet’ is exceed - NH3 and H2O
• atoms of elements in the 3rd period onwards can exceed their ‘octet’ because
they are not restricted to eight electrons in their ‘outer shell’ - S in SF6

Q.5 Show how the covalent bonding is arranged in the following molecules
a) H2 b) Cl2 c) O2 d) N2 e) NH3
f) SiCl4 g) BF3 h) SF6 i) PCl5 j) CO2

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 Structure and Bonding 7

Structures containing covalent bonds

1. Simple molecules

bonding Atoms are joined together within the molecule by covalent bonds.
electrical Don’t conduct electricity as they have no mobile ions or electrons.
solubility Tend to be more soluble in organic solvents than in water; some are hydrolysed
boiling pt Low - the forces between molecules (intermolecular forces) are weak
(known as van der Waals forces - see below)

Attractions between molecules increases as the molecules get more electrons.

e.g. CH4 -161°C C2H6 - 88°C C3H8 -42°C

as forces are weak, little energy is required

to separate molecules from each other so... boiling points are LOW

Dipole-dipole interactions (van der Waals’ forces)

Types • Induced dipole-dipole interactions - London (or Dispersion) Forces

• Permanent dipole-dipole interactions
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1. Induced dipole-dipole interactions

Origin • electrons in atoms or molecules are moving at high speeds in orbitals
• it is possible for more electrons to be on one side of an atom/molecule
• this forms a dipole where one side is slightly negative; the other slightly positive
• a dipole in one atom/molecule can then induce a dipole in a neighbouring one

For an instant there are more The dipole on one atom induces (causes) dipoles to
electrons on he right side of the form on other atoms. The atoms are then attracted to
atom - a dipole is formed each other by their oppositely charged ends

Result • atoms/molecules become attracted to each other

• this makes them harder to separate and gives them higher boiling boints

Trends • the more electrons there are in an atom/molecule the bigger the effect

Examples • layers in graphite are held together by weak van der Waals’s forces so it is soft
• the boiling point of noble gases increases down the group

Element He Ne Ar Kr Xe
No. of Electrons 2 10 18 36 54
Boiling point / °C -269 -246 -186 -152 -108

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8 Structure and Bonding

HOWEVER Some molecules have boiling points much higher than one would expect!

Electronegativity ‘The ability of an atom to attract the pair of

electrons in a covalent bond to itself.’
C—C
non polar
Non-polar bond • similar atoms have the same electronegativity
• they will both pull on the electrons to the same extent
• the electrons will be equally shared
Cδ+ — Oδ−
Polar bond • different atoms have different electronegativities polar
• one will pull the electron pair closer to its end
• it will be slightly more negative than average, δ−
• other will be slightly less negative, or more positive, δ+
• a dipole is induced and the bond is said to be polar
• the greater the electronegativity difference, the greater the bond polarity.

INCREASE

D
Pauling E
C
Scale • a scale for measuring electronegativity R TRENDS

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E
• values increase across periods A
S
E
• values decrease down groups
• fluorine has the highest value

H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Br
0.8 2.8

Q.6 Predict the polarity in the following bonds;where applicable, draw in the δ+ and δ−

a) S—Cl b) S—O

c) N—O d) C—O

e) F—Cl f) C—Cl

g) C—C

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 Structure and Bonding 9

Polar
molecules • some molecules are polar if they contain polar bonds
• the molecules will be polar if they have a NET DIPOLE MOMENT
• it is a bit like balanced forces
• non-polar molecule dipoles in bonds within the molecule ‘cancel each other’
polar molecule dipoles do not ‘cancel each other out’

δ− δ+
Cl H
δ+ δ− δ−
H — Cl δ− δ+ O
Cl C δ−
Cl H
δ− Cl δ+
NO NET DIPOLE

Experiment • place a liquid in a burette

• allow a narrow stream to run out
• place a charged rod next to the flow
• polar molecules will be attracted
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POLAR NON POLAR

Q.7 Which of the following molecules are polar?

a) F2 b) CH3Cl c) H2S d) C2H5OH e) NH3

2. Permanent dipole-dipole interaction

δ+ δ−
Occurrence • between molecules containing polar bonds H — Cl
in addition to the basic induced forces
δ+ δ−
• the extra attraction between dipoles means that H — Cl
more energy must be put in to separate molecules

• get higher boiling points than expected for a given mass

Q.8 Find the boiling points of the hydrides of elements in Groups 4,5,6, and 7.
Plot four lines (one for each group) on a graph of boiling pt. v. molecular mass.
On the graph, state what is unusual about the values for NH3, H2O and HF ?

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10 Structure and Bonding

HYDROGEN BONDING

Formation • an extension of dipole-dipole interaction giving even higher boiling points

• bonds between H and the three most electronegative elements, F, O and N
are extremely polar
• the small sizes of H, F, N and O concentrates the partial charges in a
small volume thus leading to a high charge density
• intermolecular attractions are greater, leading to even higher boiling points

Hydrogen
fluoride (HF )

WATER
Ice • each water molecule is hydrogen bonded to 4 others in a tetrahedral formation
• ice has a “diamond-like” structure
• it is a simple molecular lattice
• its volume is larger than the liquid water making it

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• when ice melts, the structure collapses slightly and molecules close together
• they then move a little further apart as they get more energy (warmer)
• this is why water has a maximum density at 4°C and ice floats.

Liquid
water • intermolecular hydrogen bonding gives higher than expected boiling point

• extra attraction between molecules just below

the surface gives a high surface tension
and causes the meniscus to be the shape it is

Viscosity The greater the hydrogen bonding in alcohols, the greater the viscosity
propan-1-ol propan-1,2-diol propan-1,2,3-triol
CH3CH2CH2OH CH3CH(OH)CH2OH CH2(OH)CH(OH)CH2OH
INCREASING VISCOSITY

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 Structure and Bonding 11

2. GIANT COVALENT LATTICES (covalent networks) - DIAMOND, GRAPHITE and SILICA

bonding Many atoms joined together in a regular array by large numbers of covalent bonds

Diamond each carbon atom is joined to four others - Co-ordination No. = 4

Graphite each carbon atom is joined to three others - Co-ordination No. = 3

melting Very high - structures are made up of a large number of covalent bonds,
point all of which need to be broken if the atoms are to be separated.

strength Diamond and silica (SiO2)

hard exists in a rigid tetrahedral structure

Graphite

soft consists of layers which are attracted

by weak induced dipole-dipole interactions

layers can slide over each other

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it used as a lubricant and in pencils

electrical Do not conduct electricity as they have no mobile ions or electrons. BUT...
Graphite conducts electricity
• each atom only uses three of its outer shell electrons for bonding to other atoms
• remaining electron can move through layers allowing the conduction of electricity
• carbon atoms in diamond use all four electrons for bonding so have no free ones

3. MOLECULAR SOLIDS

Iodine At room temperature, iodine is a grey solid. However, on gentle warming it

produces a purple vapour. This is because iodine is composed of diatomic
molecules (I2) existing in an ordered molecular crystal. Each molecule is
independent and attracted by weak induced dipole-dipole interactions.

Therefore, little energy is required to separate the iodine molecules.

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12 Structure and Bonding

DATIVE COVALENT (CO-ORDINATE) BONDING

Theory • differs from a covalent bond only in its formation

• both electrons of the shared pair are provided by one species (donor)
and it shares the electrons with the acceptor
• donor species will have lone pairs in their outer shells
• acceptor species will be short of their “octet” or maximum.

Lewis Base :- a lone pair donor Lewis Acid :- a lone pair acceptor

Formation ammonium ion, NH4+

The lone pair on N is used to +

H H
share with the hydrogen ion
which needs two electrons to + H
H N H H N
fill its outer shell. The N now
has a +ive charge as it is now H H
sharing rather than owning
two electrons.

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Boron trifluoride-ammonia NH3BF3

Boron has an incomplete

shell in BF3 and can accept a
share of a pair of electrons H
F H F

donated by ammonia. The B —

H N B F + B F
becomes -ive as it is now H N

shares a pair of electrons (i.e. H F H F

it is up one electron) it didn’t
have before.

Q.9 Why does BF3 react with NH3 but not with CH4 or AlH3 ?

Q.10 Show the formation of dative covalent bonds between

a) H2O and H+ b) AlCl3 and Cl¯ c) PCl5 and Cl¯

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 Structure and Bonding 13

Fajan’s
Rules • not all ionic compounds have high melting points
• some covalently bonded compounds have higher than expected boiling points
this is due to dipoles in their structure
• reason :- in many substances the bonding is not 100% ionic or covalent

The ideal ionic compound has completely separate,

spherical ions and the electron densities are apart
from each other.

If the positive ion has a high charge density it can

distort the negative ion by attracting the outer shell
electrons to give an area of electron density between
the two species ... a bit like a covalent bond

The feasibility of formation of covalent bonds is predicted using Fajan’s Rules.

The rules A compound is more likely to be covalent if the ...

CATION small size “highly polarising” attracts electrons in the anion

high charge
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ANION large size “highly polarisable” will be easily distorted

high charge

N.B. Just because a substance is less likely to be covalent according to Fajan’s Rules
doesn’t mean it will be ionic; it will remain covalent but have some ionic character.

Examples Changes in bond type of chlorides as the positive charge density increases due to
higher charge (across Period 3) or larger size (down Group 1)

charge ionic rad. m.pt./°C solubility bonding

Period 3 NaCl 1+ 0.095nm 808 soluble ionic
MgCl2 2+ 0.065nm 714 soluble ionic
AlCl3 3+ 0.050nm 180 hydrolysed covalent
SiCl4 4+ 0.041nm -70 hydrolysed covalent

Group 1 LiCl 1+ 0.060nm soluble some cov. character

NaCl 1+ 0.095nm soluble ionic
KCl 1+ 0.133nm soluble ionic
RbCl 1+ 0.148nm soluble ionic

Q.11 Which ion / species in each pair favours covalency ?

a) Li+ and Na+ b) Li+ and Be2+ c) B3+ and Al3+
d) F¯ and I¯ e) C and Pb f) Sn2+ and Sn4+

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14 Structure and Bonding

METALLIC BONDING
Involves a lattice of positive ions surrounded by delocalised electrons

Formation Metal atoms achieve stability by “off-loading”

electrons to attain the electronic structure of the
nearest noble gas. These electrons join up to
form a mobile cloud which prevents the newly-
formed positive ions from flying apart due to
repulsion between similar charges.

Atoms arrange themselves in regular close packed 3-dimensional crystal lattices.

The outer shell electrons of each atom leave

to join a mobile “cloud” or “sea” of electrons
which can roam throughout the metal. The
electron cloud binds the newly-formed
positive ions together.

Metallic bond strength depends on • number of outer electrons donated

• the size of the metal atom/ion.

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The melting point is a measure of the attractive forces within the metal.

electrical Conduct electricity as there are mobile electrons.

strength The delocalised electron cloud binds the “ions” together making metals ...

• malleable can be hammered into sheets

• ductile can be drawn into rods

melting pt. High. Ease of separation depends on the - density of the electron cloud and
- ionic size/charge.

PERIODS Na (2,8,1) < Mg (2,8,2) < Al (2,8,3)

m.pt 98°C 650°C 659°C
b.pt 890°C 1110°C 2470°C

reason

GROUPS Li (2,1) > Na (2,8,1) > K (2,8,8,1) > Rb > Cs

m.pt 181°C 98°C 63°C
b.pt 1313°C 890°C 774°C

reason

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